Flameproofing agents, their preparation and their use for providing polycarbonates with a flame-resistant finish

ABSTRACT

The present invention relates to phthalimide compounds of the formula (I) ##STR1## wherein X denotes H or halogen, for example chlorine or bromine, 
     a and b independently of one another denote 0 or 1 and 
     R denotes a C 1  -C 4  -alkyl radical, 
     which, in combination with alkali metal salts, are suitable as flameproofing agent combinations for thermoplastic, branched, aromatic polycarbonates, and the preparation of these compounds.

This application is a division of application Ser. No. 661,770 filedOct. 17, 1984 U.S. Pat. No. 4,661,543, 4-28-87.

The present invention relates to phthalimide compounds of the formula(I) ##STR2## wherein X denotes H or halogen, for example chlorine orbromine,

a and b independently of one another denote 0 or 1 and

R denotes a C₁ -C₄ -alkyl radical.

The present invention also relates to the preparation of phthalimides ofthe formula (I), which is characterised in that a phthalic anhydride ofthe formula (III) ##STR3## wherein X has the meaning given in the caseof formula (I), is reacted with an amine of the formula (II) ##STR4##wherein R, a and b have the meaning given in the case of formula (I), inequimolar amounts at 117° C., glacial acetic acid, as a solvent, andcyclohexane, as a water-entraining agent, also being used.

The amines of the formula (II) either are known from the literature(see, for example, U.S. Pat. No. 3,753,679) or can be obtained by theprocess described therein.

The amount of solvent to be used is about 2.5- 3.0 liters per mole ofamine employed; the amount of water-entraining agent is about 250-300 mlper mole of amine.

The new phthalimide compounds, in combination with the knownflameproofing agents for polycarbonates, that is to say the alkali metalsalts of organic or inorganic acids, are suitable synergists forimproving the flame-repellency of thermoplastic aromatic polycarbonatesprepared only from halogen-free phenolic components.

The present invention thus also relates to flameproofing agentcombinations consisting of

(a) 0.1 to 1 part by weight of a phthalimide of the formula (I) and

(b) 0.02 to 2 parts by weight of an alkali metal salt of an organic orinorganic acid, in particular a sodium, potassium or lithium salt.

Alkali metal salts of organic or inorganic acids which are suitable asflameproofing agents are mentioned, for example, in GermanOffenlegungsschriften (German Published Specifications) No. 2,703,710,No. 2,918,882 and No. 2,918,883.

The present invention also relates to the use of the flameproofing agentcombination according to the invention for providing thermoplastic,branched, aromatic polycarbonates of halogen-free phenolic componentswith a flame-repellent finish, in amounts of 0.1 to 1% by weight, basedon the thermoplastic aromatic polycarbonate, of phthalimide of theformula (I) and 0.02 to 2% by weight, based on the thermoplastic,branched, aromatic polycarbonate, of alkali metal salt of an organic orinorganic acid.

The present invention furthermore relates to a process for providingthermoplastic, branched, aromatic polycarbonates of halogen-freephenolic components with a flame-repellent finish, which ischaracterised in that the flameproofing agents are incorporated bymixing and subsequent granulation via a twin-screw extruder at amaterial temperature of 270°-300° C., preferably 270°-280° C.

The optimum processing conditions are such that a throughput of 18kg/hour is achieved at a speed of rotation of 40-80 revolutions/minute.

The twin-screw extruder used is a unit from Werner und Pfleiderer withthe designation ZSK 53.

The present invention also relates to thermoplastic mouldingcompositions based on aromatic, branched, thermoplastic polycarbonatesof halogen-free phenolic components, containing 0.1 to 1% by weight ofphthalimide of the formula (I) and 0.02 to 2% by weight of an alkalimetal salt of an inorganic or organic acid, the two ranges of thepercentages by weight each being based on the thermoplastic, branched,aromatic polycarbonate without other additives.

Aromatic, branched, thermoplastic polycarbonates of halogen-freephenolic components are to be understood as meaning that the diphenols,monophenols and trisphenols, tetraphenols or other branching agents tobe used for the preparation of the polycarbonates do not have halogensubstituents. These polycarbonates can, of course, still contain smallresidual ppm amounts of non-hydrolysed chlorine, for example if they areprepared by the phase boundary process using phosgene. In subsequentcharacterisation of the polycarbonates as "halogen-free", residues ofhalogen which can be hydrolysed in this way are not to be taken intoconsideration.

It is possible to obtain flameproofed polycarbonates with a UL 94 V-0classification with the aid of these new flameproofing agents. Cl- andBr-free flameproofed polycarbonates with V-0 in a wall thickness of 1.6mm can thus be obtained with the halogen-free phthalimides according tothe invention. V-0 is also achieved in a wall thickness of 0.8 mm byusing the halogen-containing compounds. In addition, the phthalimides ofthe formula (I) according to the invention are characterised by a lowvolatility under normal polycarbonate processing conditions.

The polycarbonate moulding compositions achieve a classification inburning class V-0, that is to say they do not drip and have an averageafter-burn time of less than 5 seconds, according to Underwriters'Laboratories Inc., Bulletin 94, Burning Tests for the Classification ofMaterials (called UL 94 below), on testpieces with dimensions of127×12.7×3.2 mm (1/8") or 127×12.7×1.6 mm (1/16") or 127×12.7×0.8 mm(1/32").

It is known that the flame repellency of polycarbonates can be improvedby addition of alkali metal salts, it being possible for thepolycarbonates to be either halogen-free or halogen-substituted. (See,for example, DE-OS (German Published Specification) No. 1,930,257, DE-OS(German Published Specification) No. 2,049,358, DE-OS (German PublishedSpecification) No. 2,112,987, DE-OS (German Published Specification) No.2,149,311, DE-OS (German Published Specification) No. 2,253,072 andDE-OS (German Published Specifications) Nos. 2,458,968, 2,461,063,2,461,146 and 2,461,077).

It is also known that the flame repellency of polycarbonates can beimproved by mixtures of organic chlorine compounds and certain inorganicsalts (see, for example, DE-OS (German Published Specification) No.2,013,496; tetrachlorophthalic anhydride, inter alia, is mentioned as asuitable organic chlorine compound).

It is also known that polycarbonates can be rendered flame-repellentwith brominated phthalimides (see U.S. Pat. No. 3,873,587).

It is also known that phthalimide compounds can be used in combinationwith alkali metal salt additives, exclusively halogenated phthalimidesbeing employed (DOS (German Published Specification) No. 2,707,928, DOS(German Published Specification) No. 2,740,850 and DOS (German PublishedSpecification) No. 2,703,710).

It is also known that organic halogen compounds, such as halogenatedphthalimides, can be used in combination with alkali metal salts andwith substances which reduce the tendency of polycarbonates to drip, forproviding polymer blends based on polycarbonates with a flame-repellentfinish. (See DE-OS (German Published Specification) No. 2,918,882 andDE-OS (German Published Specification) No. 2,918,883.)

It is also known that moulding compositions of branched aromaticpolycarbonates can be provided with a flame-repellent finish for extremeflaming conditions together with alkali metal salts and halogenatedphthalimides and an additional bromine content. (See DE-OS (GermanPublished Specification) No. 3,203,905.)

However, in our opinion, the literature references mentioned neitheranticipate nor suggest either the phthalimides of the formula (I) ortheir use as a flameproofing synergist for halogen-free polycarbonates.

Furthermore, no additive combinations have hitherto been disclosedwhich, after admixing of such small amounts by weight of a chlorine-freeand bromine-free phthalimide, already give polycarbonate mouldingcompositions of burning classes V 0 according to UL 94 at 1/8" and1/16", and, using halogen-containing products, at 1/32" wall thickness.

The admixture claimed according to the invention of phthalimides of thegeneral formula (I) is therefore particularly advantageous becausecompounds of these classes of substance are very stable to heat, have alow volatility, are stable to hydrolysis and can easily be mixed intopolycarbonate.

Examples of suitable alkali metal salts of inorganic acids in thecontext of the invention are those of inorganic proton acids. Inorganicproton acids in the context of the invention are Bronsted acids whichcan form alkali metal salts (on the term ∓Bronsted acid", compare Fieser& Fieser "Organic Chemistry", 1965, page 595, Interscience Publishers,N.Y., USA), such as, for example, meta-, ortho- or pyro-phosphoric acidsand proton acids of complex fluorometallic compounds.

Suitable alkali metal salts of organic acids in the context of theinvention are those of organic Bronsted acids with at least one carbonatom which can form alkali metal salts. Such optionally substitutedorganic acids can be OH-- or NH--acid compounds, such as, for example,sulphonic acids, phosphonic acids, thiophosphonic acids and NH-acidsulphonamides or sulphonimides. They must have at least one C atom andcan preferably contain between 2 and 30 C atoms.

The alkali metal salts which are suitable according to the inventionshould preferably have a pH value of between 5 and 9, in particularbetween 6.5 and 7.5, measured on 1% strength by weight solutions orsuspensions of the salts in water at 20° C.

Preferred alkali metal salts are the potassium, sodium and lithiumsalts, in particular the potassium salts.

Preferred alkali metal salts of organic acids are the sodium, potassiumand lithium salts, but in particular the potassium salts of organicsulphonic acids and phosphonic acids, the organic radicals of which canbe optionally substituted by halogens, such as fluorine, chlorine orbromine. Examples which may be mentioned are: sodium or potassiumperfluorobutanesulphonate, sodium or potassiumperfluoromethanesulphonate, sodium or potassium2,5-dichlorobenzenesulphonate, sodium or potassium2,4,5-trichlorobenzenesulphonate, sodium or potassium(4-chlorophenyl)phosphonate, sodium or potassium methyl-phosphonate,sodium or potassium (2-phenylethyl)-phosphonate and lithium,phenyl-phosphonate.

Preferred alkali metal salts of inorganic acids are the sodium,potassium and lithium salts, but in particular the potassium salts ofproton acid complexes, such as fluorometallic compounds, and of meta-,ortho or pyrophosphoric acids.

Examples which may be mentioned are: trisodium or tripotassiumhexafluoroaluminate, disodium or dipotassium hexafluorotitanate,disodium or dipotassium hexafluorosilicate, disodium or dipotassiumhexafluorozirconate, sodium or potassium pyrophosphate, sodium orpotassium metaphosphate, sodium or potassium tetrafluoborate, sodium orpotassium hexafluorophosphate and sodium, potassium or lithiumphosphate.

Particularly suitable salts are: potassium or sodiumperfluorobutanesulphonate, potassium or sodium2,5dichlorobenzenesulphonate, potassium or sodium2,4,5-trichlorobenzenesulphonate, potassium hexafluoroaluminate,potassium pyrophosphate, potassium methyl-phosphonate, sodiumhexafluoroaluminate and lithium phenyl-phosphonate.

Mixtures of the salts with one another are also suitable.

Halogen-free aromatic, branched, thermoplastic polycarbonates in thecontext of the present invention are polycondensates which can beobtained by reacting halogenfree diphenols, in particulardihydroxydiarylalkanes, with phosgene or diesters of carbonic acid,dihydroxydiarylalkanes in which the aryl radicals carry alkyl groups inthe o- and/or m-position relative to the hydroxyl group also beingsuitable, in addition to the unsubstituted dihydroxydiarylalkanes; thesepolycondensates are branched by incorporation of between 0.05 and 2.0mole % (based on the diphenols employed) of compounds which aretrifunctional or more than trifunctional, for example those with threeor more than three phenolic hydroxyl groups.

Polycarbonates of this type and their preparation are described, forexample, in German Offenlegungsschriften (German PublishedSpecifications) Nos. 1,570,533, 1,595,762, 2,116,974 and 2,113,347,British Pat. Specification No. 1,079,821, U.S. Pat. Specification No.3,544,514 and German Offenlegungsschrift (German PublishedSpecification) No. 2,500,092.

The halogen-free aromatic, branched, thermoplastic polycarbonates haveweight-average molecular weights Mw of between 15,000 and 100,000,preferably between 20,000 and 80,000, determined by measurement of therelative viscosity in CH₂ CL₂ at 25° C. and a concentration of 0.5 g/100ml, after appropriate calibration.

Examples of suitable halogen-free diphenols are hydroquinone,resorcinol, 4,4'-dihydroxydiphenyl, bis(hydroxy-phenyl)-alkanes, suchas, for example, C₁ -C₈ -alkylene- or C₂ -C₈ -alkylidene-bisphenols,bis-(hydroxy-phenyl)-cycloalkanes, such as, for example, C₅ -C₁₅-cycloalkylene- or C₅ -C₁₅ cycloalkylidene-bisphenols, andbis-(hydroxy-phenyl) sulphides, ethers, ketones, sulphoxides orsulphones, furthermore, α,α'-bis-(hydroxyphenyl)-diisopropylbenzene andthe corresponding nuclear-alkylated compounds. Polycarbonates based on2,2-bis-(4-hydroxy-phenyl)-propane (bisphenol A),2,2-bis-(4-hydroxy-3,5-di-methylphenyl)-propane (tetramethylbisphenol A)or 1,1-bis-(4-hydroxy-phenyl)-cyclohexane (bisphenol Z) and those basedon trinuclear bisphenols, such asα,α'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene are preferred.

Other halogen-free diphenols which are suitable for the preparation ofthe polycarbonates are described in U.S. Pat. Nos. 3,028,365 and3,275,601.

Examples of some of the compounds which have three or more than threephenolic hydroxy groups and which can be used are phloroglucinol,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)phenylmethane,2,2-bis-/4,4-bis-(4-hydroxyphenyl)-cyclohexyl/propane,2,4-bis-(4-hydroxyphenyl-isopropyl)phenol,2,6-bis-(2'-hydroxy-5'-methyl-benzyl)-4-methylphenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,hexa(4-(4-hydroxyphenyl-isopropyl)-phenyl)-ortho-terephthalic acidester, tetra-(4-hydroxyphenyl)-methane,tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy)-methane and1,4-bis-(4',4"-dihydroxytriphenyl)-methyl)-benzene. Some of the othertrifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid,cyanuric chloride, 3,3-bis-(4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and3,3-bis-(4-hydroxy-3-methyl-phenyl)-2-oxo-2,3-dihydroindole.

Suitable chain stoppers for regulating the molecular growth are, forexample, in the known manner, phenol and alkylphenols, which are used inthe known amounts.

The aromatic, branched, thermoplastic polycarbonates are prepared in aknown manner, for example by the phase boundary process or by theprocess in homogeneous solution. The aromatic, thermoplasticpolycarbonates can also be prepared by the known transesterificationprocess.

Particularly preferred polycarbonates in the context of the presentinvention are branched polycarbonates based on bisphenol A with abranching agent content of 0.3 to 1.0 mole %, based on the moles ofbisphenol A.

A suitable amine of tne formula II is ##STR5##

This compound is described in U.S. Pat. No. 3,753,679.

Suitable phthalimide compounds of the formula I are ##STR6##

These compounds can be prepared by the process in the examples and underthe general process conditions mentioned above.

The flameproofing agents according to the invention can be preparedbeforehand by mixing the individual components or as a concentrate inthe polycarbonate and stored until they are used.

The new flameproofing agent combination can be incorporated into thepolycarbonates in the form of its individual components or as a whole,for example by mixing and subsequent granulation of the material via atwin-screw extruder at 270° to 280° C.

The moulding compositions according to the invention based onpolycarbonate and flameproofing agent combination can also contain otheradditives customary in polycarbonate chemistry, such as, for example,pigments, dyestuffs, fillers, stabilisers or mould release agents.

The moulding compositions according to the invention can be processed toshaped articles or films.

Shaped articles are produced by the injection-moulding process at atemperature of 300°-310° C.

The moulding compositions according to the invention can be used, forexample, in the electrical field for switch shields, sockets, socketpanels, switchboxes and the like, in the domestic sector for housingcomponents for irons and coffee machines and in the large appliancefield, for example, for computer housing components.

Description of the Burning Test

According to the UL 94 test (Underwriter's Laboratories, Inc.),polycarbonate samples are shaped to bars having dimensions of127×12.7×3.2 (or 1.6 or 0.8) mm (5.00×0.5×1/8 (or 1/16 or 1/32) inches.The bars are mounted vertically so that the underside of the testpieceis 305 mm above a strip of bandaging material. Each test bar is ignitedindividually by means of two successive ignition operations lasting 10seconds, the burning characteristics are observed after each ignitionoperation and the sample is then evaluated. A Bunsen burner with a 10 mm(3/8 inch) high blue flame of natural gas with a heat content of3.73×10⁴ kJ/m³ 1.000 BTU per cubic foot) is used for igniting thesample.

The UL 94 V 0 classification concerns the properties, described below,of materials which have been tested in accordance with the UL 94specification. The polycarbonates in this class contain no samples whichburn for longer than 10 seconds after each action of the test flame;they show no total flaming time of more than 50 seconds on two actionsof the flame on each set of samples; they contain no samples which burncompletely up to the holding clamp attached at the top end of thesample; they contain no samples which ignite the cottonpool placed belowthe sample by burning drops or particles; they also contain no sampleswhich glow for longer than 30 seconds after the test flame has beenremoved.

Other UL 94 classifications designate samples which are lessflame-repellent and self-extinguishing and which give flaming drops orparticles. These classifications are designated UL 94 V 1 and V-2.

The polycarbonates within the scope of this invention characteristicallyshow the properties required for UL94 V-0 classification.

EXAMPLES A. Preparation pf Phthalimides of the Formula (I) A.1Preparation of a Phthalimide of the General Formula (I) usingtetrachlorophthalic anhydride

1,600 ml of glacial acetic acid are initially introduced into athree-necked flask provided with a thermometer, stirrer and waterseparator, and are warmed to 55° C. A mixture of 171.6 g (0.6 mole) oftetrachlorophthalic anhydride and 157.8 g (0.6 mole) of3-amino-4-methoxydiphenyl sulphone is then added and the mixture isstirred vigorously. The reaction mixture is kept under reflux at 118° C.for 2.5 hours and is then cooled. After addition of 150 ml ofcyclohexane, the reaction mixture is kept under reflux for 6 hours,during which the water of reaction can be removed in the waterseparator.

The resulting solid is filtered off hot with suction, rinsed withglacial acetic acid, suspended in hot acetone and dried.

% N theory: 2.64; % C theory: 47.5; % H theory: 2.1 % Cl theory: 26.7. %N found: 2.86; % C found: 47.5; % H found : 2.05 % Cl found: 26.5.

A.2 Preparation of a Phthalimide of the General Formula (I) usingphthalic anhydride

The phthalimide is prepared according to A 1, using phthalic anhydride.

% N theory: 3.56; % C theory: 64.1; % H theory: 3.82% N found: 3.54; % Cfound: 64.0; % H found : 3.84.

B. Flame-Repellent, Branched Polycarbonates

A branched polycarbonate based on bisphenol A, 0.5 mole % of3,3-bis-(4-hydroxy-3-methylphenyl)-2-oxo-2,3-dihydroindole, 3.0 mole %of phenol, as a chain stopper, and phosgene having a solution viscosityof 1.31 (measured in CH₂ CL₂ at 250° C. and in a concentration of 0.5g/100 ml) was mixed with 0.1% of the K salt ofn-perfluorobutanesulphonic acid or with the phthalimides according tothe invention and the mixture was extruded and its fire repellency wasexamined according to UL 94 in thicknesses of 3.2 mm, 1.6 mm and 0.8 mm.

The following table shows the result:

    ______________________________________                                        Examples:                                                                     PC (B) PFS    PI     Cl PI         UL 94 V                                    %      %      %      %      3.2 mm 1.6 mm 0.8 mm                              ______________________________________                                        99.9   0.1                  V-0    V-2    V-2                                 99.4   0.1    0.5           V-0    V-0    V-2                                 99.4   0.1           0.5    V-0    V-0    V-0                                 ______________________________________                                         PC (B): polycarbonate according to Example B                                  PFS: K salt of nperfluorobutanesulphonic acid                                 PI: phthalimide based on 3amino-4-methoxy-diphenyl sulphone according to      A.2                                                                           Cl PI: tetrachlorophthalimide based on 3amino-4-methoxy-diphenyl sulphone     according to A.1                                                         

We claim:
 1. A phthalimide of the general formula ##STR7## wherein Xdenotes hydrogen or up to four halogen atoms,a and b independently ofeach other denote 0 or 1 and R denotes a C₁ -C₄ -alkyl radical.
 2. Aphthalimide according to claim 1 having the following formula ##STR8##3. A phthalimide according to claim 1, having the following formula##STR9##
 4. A process for the production of a phthalimide according toclaim 1 in which a phthalic anhydride of the general formula ##STR10##wherein X has the same meaning as in claim 1, is reacted with an amineof the general formula ##STR11## wherein R,a and b have the samemeanings as in claim 1, in substantially equimolar amounts at 117° C.,in the present of glacial acetic acid, as solvent and cyclohexane, as awater-entraining agent.
 5. A process according to claim 4, in which theglacial acetic acid is present in an amount of 2.5 to 3.0 liters permole of amine of formula (II).
 6. A process according to claim 4, inwhich the cyclohexane is present in an amount of 250 to 300 ml per moleof amine of formula (II).
 7. A process according to claim 4, in whichthe amine of formula (II) is a compound of the formula ##STR12##
 8. Thephthalimide produced by the process of claim 4.